Cross-linkable polyurethane block copolymers and their use in dispersion binding agent systems

ABSTRACT

The invention relates to polyurethane block copolymers of general formula (I) to (IV), in which the variables are defined as follows: A represents a polyurethane block, which contains at least one hydrophilic group, B is a hydrophobic polyurethane block, X 1 , X 2  are hydrophilic end groups and n is a whole number from 1 to 20. The invention also relates to the production of cross-linkable dispersion additives from the inventive polyurethane block copolymers and to the use of said cross-linkable dispersion additives for colorant preparations, in particular inks for ink-jet printing.

The present invention relates to polyurethane block copolymers of thegeneral formulae I to IV

where:

-   A is a polyurethane block containing at least one hydrophilic end    group X¹,-   B is a hydrophobic polyurethane block,-   X¹ and X² are each a hydrophilic end group, and-   n is an integer from 1 to 20.

The present invention further relates to crosslinkable dispersing bindersystems comprising the polyurethane block copolymers of the inventionand melamine derivatives, the use of the dispersing binder systemsaccording to the invention for producing colorant preparations and thethus obtainable colorant preparations. The present invention furtherprovides for the use of the colorant preparations according to theinvention in aqueous and nonaqueous inks for ink jet printing, aqueousand nonaqueous inks for the ink jet printing process, comprising thecolorant preparations according to the invention, and also a process forprinting sheetlike substrates by the ink jet process using the inksaccording to the invention. The present invention lastly provides forthe use of the dispersing binder systems according to the invention inwaterborne coatings, high solids coating systems, solvent-containingcoatings, no solvent or low solvent coatings, no solvent or low solventpaints and nonaqueous inks comprising the dispersing binder systemsaccording to the invention.

Inks for use in the ink jet process (such as Piezo Ink Jet, ContinuousInk Jet, Valve Jet) have to meet a whole series of requirements. Theyhave to have a viscosity and surface tension suitable for printing, theyhave to be stable in storage, i.e., they should not coagulate orflocculate, and they must not lead to cloggage of the printer nozzle,which can be problematical especially in the case of inks containingdispersed, i.e., undissolved, colorant particles. Stability in storagefurther requires of these inks that the dispersed colorant particles donot sediment. Furthermore, in the case of Continuous Ink Jet the inksshall be stable to the addition of conducting salts and be free from anytendency to flock out with an increase in the ion content. In addition,the prints obtained have to meet colorists' requirements, i.e., showbrilliance and depth of shade, and have good fastness properties, forexample, lightfastness, and good drying characteristics.

These requirements can be met by means of suitable dispersing additives.The literature discloses various dispersing additives whose propertieshave to be further optimized, however.

After a substrate, for example a textile substrate, has been printed,the inks should remain on the substrate and should certainly not beredispersed in a wash liquor used for washing the textile for example.This requires the addition of a binder to the ink or a correspondingtreatment of the textile shortly before or after printing, and thisrequires an additional operation.

WO 00/17250 describes the use of dispersants having a block copolymerstructure consisting of a di- or polyfunctional isocyanate and a blockwhich is terminated with a polar group, for example COOH, and whose endgroup has been reacted with for example polyamides or vinyl-bearingN-containing heterocycles. Inks produced using such dispersants havevery good properties with regard to rubfastness and waterfastness, butin the case of prints on textile the level of fixation reveals a needfor optimization after several washes. Similarly, fixation decreasessubstantially in the case of substrates which are bent, folded orcreased.

WO 99/41320 describes ink jet printing inks dispersed usingpolyurethanes having for example dimethylolpropionic acid orpolyethylene monomethyl ether as dispersing groups, randomly distributedacross the molecule. The inks produced using the inks described arenotable for good storage stability and good to moderate printingproperties, especially with regard to nozzle failure, but the fixationof the prints is too low for commercial applications.

WO 99/50364 describes the use of polyurethanes as dispersants in ink jetinks comprising a water-soluble solvent, a water-insoluble solvent andwater. The polyurethanes contain dispersing, i.e., water-solubilizing,groups randomly distributed across the molecule. However, the fixationof the ink is still capable of improvement.

EP-A 0 739 959 describes random polyurethane copolymers and their use asdispersants.

WO 00/03081 describes a process for printing textile substrates usingthe ink jet printing process by pretreatment of the substrate with abinder. This process requires an additional operation. It iseconomically sensible to develop an ink which renders this additionaloperation unnecessary. However, prior art dispersants are not useful asan ingredient of these inks.

It is an object of the present invention to provide novel dispersingbinder systems which overcome the prior art disadvantages and provide asimple process for printing textile substrates. It is a further objectof the present invention to use the novel dispersing binder systems toproduce inks and to provide a process of production using the novelinks. It is yet a further object of the present invention to printtextile substrates using the novel inks, especially by the ink jetprocess.

Pigment dyeing is a process whereby dyeing liquors containing binder aswell as pigment are generally applied to textile substrates by a paddingoperation with subsequent drying and fixing. The advantage of thisoperation is the low water consumption, since no further washingoperations are needed, which is an ecological advantage. Thedisadvantage is the inability to provide deep shades if fastness andtextile hand are to be satisfactory.

It is a further object of the present invention to provide noveldispersing binders which do not have the disadvantages of the prior artand which make possible a simple process for printing and dyeing textilesubstrates.

We have found that these objects are achieved by the polyurethane blockcopolymers defined at the beginning and their use as dispersing bindersystems.

The polyurethane block copolymers of the present invention are blockcopolymers of the general formulae I to IV where:

-   A is a polyurethane block containing at least one hydrophilic end    group X¹,-   B is a hydrophobic polyurethane block,-   X¹ and X² are each a hydrophilic end group, and-   n is an integer from 1 to 20.

Polyurethanes for the purposes of the present invention are not onlypolymers which are exclusively linked by urethane groups but in a moregeneral sense polymers which are obtainable by reaction of di- orpolyisocyanates with compounds containing active hydrogen atoms.Polyurethanes for the purposes of the present invention, as well asurethane groups, can also contain urea, allophanate, biuret,carbodiimide, amide, ester, ether, uretonimine, uretidione, isocyanurateor oxazolidine groups. An example of a survey isKunststoffhandbuch/Saechtling, 26th edition, Carl-Hanser-Verlag, Munich1995, page 491 ff. More particularly, polyurethanes for the purposes ofthe present invention can contain urea groups. However, polyurethanesfor the purposes of the present invention contain at least one urethanegroup.

Block A has a formula weight M_(n) from 600 to 30 000 g, preferably upto 10 000 g, more preferably up to 5000 g and most preferably up to 2000g.

Block B has a formula weight M_(n) from 600 to 30 000 g, preferably upto 10 000 g, more preferably up to 5000 g and most preferably up to 2000g.

Hydrophilic end groups X² in the polyurethane block copolymers of thegeneral formula III according to the invention are identical ordifferent groups selected from:

—OH, O(CH₂—CH₂—O)_(x)—H, —O(—CHCH₃—CH₂—O)_(x)—H, —O(—CH₂—CHCH₃—O)_(x)—H,—O(—CH₂—CH₂—CH₂—CH₂—O)_(x)—H, where x is an integer from 1 to 20,preferably from 1 to 10 and more preferably from 1 to 5; SO₃—, COOH.

Polyurethane block copolymers of the general formulae I, II and IV arepreferred. Particular preference is given to polyurethane blockcopolymers of the general formula I. The construction and synthesis ofthe polyurethane block copolymers of the present invention could now beillustratively described with reference to compounds of the formula I.

The first step is to prepare blocks A and B in separate operations. Toprepare the hydrophobic block B, one or more diisocyanates are reactedby known methods with one or more compounds bearing twoisocyanate-reactive groups. The NCO groups of the diisocyanate ordiisocyanates can have the same or a different reactivity. Examples ofdiisocyanates having NCO groups of the same reactivity aromatic oraliphatic diisocyanates, preference being given to aliphaticdiisocyanates such as tetramethylene diisocyanate, hexamethylenediisocyanate, octamethylene diisocyanate, decamethylene diisocyanate,dodecamethylene diisocyanate, tetradecamethylene diisocyanate,trimethylhexane diisocyanate, tetramethylhexane diisocyanate, 1,4-, 1,3-or 1,2-diisocyanatocyclohexane, 4,4′-di(isocyanato-cyclohexyl)methane,1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophoronediisocyanate) and 2,4- and 2,6-diisocyanato-1-methylcyclohexane, ofwhich hexamethylene diisocyanate and isophorone diisocyanate areparticularly preferred. A further particularly preferred diisocyanate ism-tetramethylxylene diisocyanate (TMXDI).

Preferred diisocyanates having NCO groups of differing reactivity arethe readily and inexpensively available isocyanates such as for example2,4-toluylene diisocyanate (2,4-TDI), 2,4′-diphenyl-methane diisocyanate(2,4′-MDI), triisocyanatotoluene as representatives of aromaticdiisocyanates or aliphatic diisocyanates, such as2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexylisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate,2,4′-methylenebis-(cyclohexyl) diisocyanate and 4-methylcyclohexane1,3-diisocyanate (H-TDI).

Further examples of isocyanates having groups differing in reactivityare 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,1,5-naphthylene diisocyanate, diphenyl diisocyanate, toluidinediisocyanate and 2,6-tolylene diisocyanate.

It will be appreciated that mixtures of two or more of theaforementioned isocyanates can also be used.

It is also possible to replace fractions of the diisocyanate withpolyisocyanates, for example triisocyanate or tetraisocyanate, in orderthat branches may be incorporated into the polyurethane block.

Examples of compounds bearing two isocyanate-reactive groups such as forexample OH, SH, NH₂ or NHR, where R is selected from C₁–C₁₂-alkyl, arefor example diols and secondary diamines. Preferred examples aresecondary diamines, for example 1,4-butylene-N,N′-dimethylamine, andespecially linear or branched alkanediols or cycloalkanediols havingfrom 2 to 10 carbon atoms in the alkylene moiety; preferred candidatesare in particular: ethylene glycol, 1,2-propanediol, 1,3-propanediol,1,4-butanediol, 1,6-hexanediol, neopentyl glycol,cis-1,2-cyclohexanedimethanol, trans-1,2-cyclohexanedimethanol and alsotrans-1,4-cyclohexanedimethanol. It is also possible to use mixtures ofthe aforementioned compounds. It is further possible to use compoundscontaining various isocyanate-reactive groups, for example thioglycol orethanolamine or methyldiethanolamine.

Suitable catalysts to speed especially reaction between the NCO groupsof the diisocyanates and the hydroxyl groups and amino groups of thecompounds bearing two isocyanate-reactive groups are the well-knowntertiary amines, for example triethylamine, dimethylcyclohexylamine,N-methylmorpholine, N,N′-dimethylpiperazine,2-(dimethylaminoethoxy)ethanol, diazabicyclo(2,2,2)octane and the likeand especially organic metal compounds such as titanate esters, ironcompounds such as for example iron(III) acetylacetonate, tin compounds,for example tin diacetate, tin dioctoate, tin dilaurate or the dialkylderivatives of tin dialkyl salts of aliphatic carboxylic acids such asdibutyltin diacetate, dibutyltin dilaurate or the like. The catalystsare customarily used in amounts from 0.0001 to 0.1 part by weight per100 parts by weight of diol or diamine.

The diisocyanates are used in an excess such that the B block isobtained in such a way that it attains the desired molecular weightwhile still bearing two NCO groups capable of reaction with compoundsbearing active hydrogen atoms.

To prepare compounds of the general formula II or III or IV, ahydrophobic block is prepared with one or—in the case of compounds ofthe formula IV—n NCO groups.

The synthesis of block B is generally carried out without a solvent orin an aprotic solvent, for example in tetrahydrofuran, diethyl ether,diisopropyl ether, chloroform, dichloromethane, di-n-butyl ether,acetone, N-methylpyrrolidone (NMP), xylene, toluene, methyl ethyl ketone(MEK), methyl isobutyl ketone (MIBK) or 1,4-dioxane. Preferred reactiontemperatures are in the range from 10° C. to the boiling point of thesolvent used. The reaction is generally carried out under atmosphericpressure, but it may also be carried out in autoclaves at up to 20 bar.

To prepare a hydrophobic block B having n NCO groups, branches areincorporated in the polyurethane chain. This is accomplished by addingone or more triisocyanates such as for example Basonat® HB100 to thediisocyanate. Alternatively, the diol can be mixed with one or moretriols or tetraols such as for example glycerol, trimethylolpropane orpentaerythritol.

The above-described hydrophobic block is subsequently linked via the NCOgroups to one, two or n hydrophilic polyurethane blocks.

The hydrophilic polyurethane block A is synthesized similarly to theabove-described block B, except that the compound which bears twoisocyanate-reactive groups is used in excess, so that A is produced asan OH—, SH—, NH₂— or NHR-terminated block or as a mixture of OH—, SH—,NH₂— or NHR-terminated blocks, where R is selected from C₁–C₁₂-alkyl orC₆–C₁₄-aryl.

Useful diisocyanates include the abovementioned diisocyanates, andm-tetramethylxylene diisocyanate (TMXDI) is most preferred.

As well as diisocyanates and diols, the polyurethane block A hasincorporated into it hydrophilic end groups X¹, at least one per block.The hydrophilic end groups are preferably carboxyl groups, which can beintroduced for example by means of dihydroxycarboxylic acids such asdimethylolpropionic acid (DMPA) or citric acid. Another embodiment ofthe present invention introduces a sulfo-containing diol, for examplethe Michael adduct of diethanolamine with acryloylaminopropanesulfonicacid. Dimethylolpropionic acid is a most preferred example. It isfurther possible to incorporate selected diols as additional hydrophiliccomponents: polyethylene glycols having from 2 to 50 ethylene units anda preferred molecular weight M_(n) in the range from 900 to 2 000 g,polypropylene glycols having from 2 to 20 propylene units,polytetrahydrofuran derivatives having from 2 to 10 tetramethylene unitsand also polyesterpolyols, preferably polyesterdiols. Polyesterpolyolsare saturated polyesters or polyethers with or without ether groups thatcontain at least two free hydroxyl groups per molecule, and preferablythey contain from two to ten and more preferably precisely two freehydroxyl groups per molecule. The average formula weights M_(n) of thepolyesterpolyols range from 250 to 4000 g and preferably from 450 to2000 g.

Such polyesterpolyols are obtainable for example in conventional mannerby esterification of one or more dicarboxylic acids or tricarboxylicacids or mixtures of dicarboxylic acids with tricarboxylic acids withdiols or triols. The esterification can be carried out in the absence ofa solvent or else by azeotropic esterification in the presence of anentrainer. The starting materials for polyesterpolyols are known to oneskilled in the art. Preferred dicarboxylic acids include succinic acid,glutaric acid, adipic acid, sebacic acid, pimelic acid, ortho-phthalicacid or their isomers and hydrogenation products and also esterifiablederivatives thereof, for example anhydrides or dialkyl esters, forexample dimethyl esters or diethyl esters. Preferred diols includeethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol,1,6-hexanediol, neopentylglycol, cis-1,2-cyclohexanedimethanol,trans-1,2-cyclohexanedimethanol, polyglycols of the ethylene glycol and1,2-propanediol type and also diols having at least one furtherfunctional group such as for example dimethylolpropionic acid.

Preferred triols are glycerol and trimethylolpropane.

Useful diols further include polycaprolactonediols andpolycaprolactonetriols, the preparation of which is likewise known toone skilled in the art.

Useful polyether polyols include for example reaction products ofdihydric and/or higher alcohols with one or more equivalents of ethyleneoxide and/or propylene oxide. In the case of ethylene oxide-propyleneoxide intercondensation products, the reaction can conveniently becontrolled so that predominantly primary hydroxyl groups are obtained inthe terminal positions. It is further possible to use polybutyleneoxides. The average formula weights M_(n) of the polyetherpolyols rangefrom 250 to 4000 g and preferably from 450 to 2000 g.

The synthesis of the polyurethane block A is generally carried outwithout a solvent or in an aprotic solvent, for example intetrahydrofuran, diethyl ether, diisopropyl ether, chloroform,dichloromethane, di-n-butyl ether, acetone, N-methylpyrrolidone (NMP),xylene, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone(MIBK) or 1,4-dioxane. Preferred reaction temperatures are in the rangefrom 10° C. to the boiling point of the solvent used. The reaction isgenerally carried out under atmospheric pressure, but it may also becarried out in autoclaves at up to 20 bar.

The hydrophilic end groups X¹ described are absent from the hydrophobicblock B. The polyurethane block copolymers of the invention are obtainedby reacting the hydrophobic block B with 2 equivalents of block A in thepresence of a compound catalyzing urethane formation, for exampletriethylamine, dimethylcyclohexylamine, N-methylmorpholine,N,N′-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol,diazabicyclo(2,2,2)octane and the like and also especially organic metalcompounds such as titanate esters, iron compounds such as for exampleiron(III) acetylacetonate, tin compounds, for example tin diacetate, tindioctoate, tin dilaurate or the dialkyl derivatives of tin dialkyl saltsof aliphatic carboxylic acids such as for example dibutyltin diacetateor dibutyltin dilaurate in amounts from 0.0001 to 0.1 part by weight per100 parts by weight of diol or diamine.

To obtain the polyurethane block copolymers of the general formulae IIor III according to the invention, block B is respectively reacted withone or n+1 equivalents of A.

Blocks A and B are generally linked according to the invention by knownmethods without a solvent or in one of the solvents mentioned above.Preferred reaction temperatures range from 10° C. to the boiling pointof the solvent used. The reaction is generally carried out underatmospheric pressure, but reactions in autoclaves at up to 20 bar arealso possible.

To further use the polyurethane block copolymers of the general formulaeI to IV according to the invention, strongly acidic hydrophilic groupssuch as carboxyl groups and sulfonic groups are neutralized with bases.Preferably they are neutralized with volatile bases such as for exampleammonia or volatile primary, secondary or tertiary amines, for examplemethylamine, ethylamine, dimethylamine, diethylamine, trimethylamine,triethylamine, isopropylamine, ethyldiisopropylamine, di-n-butylamine,ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine,n-propyldiethanolamine or n-butyldiethanolamine.

The present invention further provides melamine-containing polyurethaneblock copolymers and also a process for producing same from theabove-described crosslinkable polyurethane block copolymers, by mixingthe above-described polyurethane block copolymers of the generalformulae I to IV with one or more melamine derivatives of the generalformula V

where R¹ to R⁶ are the same or different and are each selected from:hydrogen orCH₂—OR⁷, CH(OR⁷)₂ and CH₂—N(R⁷)₂,where each R⁷ may be the same or different and is selected fromhydrogen,C₁–C₁₂-alkyl, branched or unbranched, for example methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl, n-decyl andn-dodecyl; preferably C₁–C₆-alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl,isohexyl, sec-hexyl, particularly preferably C₁–C₄-alkyl such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;alkoxyalkylene selected from (—CH₂—CH₂—O)_(m)—H, (—CHCH₃—CH₂—O)_(m)—H,(—CH₂—CHCH₃—O)_(m)—H, (—CH₂—CH₂—CH₂—CH₂—O)_(m)—H, where m is an integerfrom 1 to 20, preferably from 1 to 10 and more preferably from 1 to 5.

R¹, R³ and R⁵ are preferably different.

Particularly preferably R¹ and R² are both hydrogen and R³ and R⁴ areboth CH₂—OH. Most preferably, R¹ and R² are both hydrogen and R³ isCH₂—OH.

Melamine derivatives of the general formula V are known per se and arecommercially obtainable for example as Luwipal® from BASFAktiengesellschaft and as Cymel® 327 from Cytec. Melamine derivativesfor the purposes of the present invention are generally not pure inaccordance with any defined formula; it is usual to observeintermolecular rearrangements of R¹ to R⁶, i.e., transacetalizationreactions and transaminalization reactions, and also to some extentcondensation reactions and elimination reactions. The formula Vindicated above is to be understood as defining the stoichiometricratios of the substituents and as also encompassing intermolecularrearrangement products and condensation products and eliminationproducts.

The polyurethane block copolymers and melamine derivatives of thegeneral formula V according to the invention are customarily used in aweight ratio in the range from 0.01:1 to 100:1, preferably from 0.1:1 to50:1 and more preferably from 1:1 to 10:1.

The present invention further provides crosslinkable dispersing bindersystems which are obtainable by the above process by mixing thepolyurethane block copolymers of the general formulae I to IV and one ormore melamine derivatives of the general formula V.

The colorant preparations according to the invention are obtained byintensively mixing the dispersing binder systems according to theinvention with one or more sparingly water-soluble colorants, forexample in a ball mill. The colorant preparations according to theinvention are preferably prepared by not isolating the crosslinkabledispersing binder systems and mixing the synthesized polyurethane blockcopolymers of the general formulae I to IV with one or more melaminederivatives of the general formula V, water and one or more sparinglywater-soluble colorants, for example in a ball mill, at pressures from 1to 10 bar and from 0 to 250° C. Ball-milled colorant preparations arealso known as grinds.

The colorant preparations according to the invention, as well as thecrosslinkable polyurethane block copolymers, include water and alsofinely divided organic or inorganic colorants, i.e., pigments as definedin German standard specification DIN 55944, that are dispersed andsubstantially insoluble in water and/or in the water-solvent mixture. Itwill be appreciated that the colorant preparations of the invention mayalso include colorant mixtures, but preferably only one colorant ispresent. By way of brightening agents, these pigment preparations mayinclude dyes, especially direct, acid or reactive dyes, that are similarin hue to the pigment.

There now follow examples of useful pigments, vat dyes being includedamong the organic pigments on account of the overlap with organicpigments.

Organic pigments:

monoazo pigments: C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48:1,48:2, 48:3, 48:4, 49, 49:1, 52:1, 52:2, 53, 53:1, 53:3, 57:1, 63, 112,146, 170, 184, 210, 245 and 251; C.I. Pigment Yellow 1, 3, 73, 74, 65,97, 151 and 183; disazo pigments: C.I. Pigment Orange 16, 34 and 44;C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment Yellow 12, 13, 14,16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188; anthanthronepigments: C.I. Pigment Red 168 (C.I. Vat Orange 3); anthraquinonepigments: C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31;anthraquinone pigments: C.I. Pigment Yellow 147 and 177; C.I. PigmentViolet 31; anthrapyrimidine pigments: C.I. Pigment Yellow 108 (C.I. VatYellow 20); quinacridone pigments: C.I. Pigment Red 122, 202 and 206;C.I. Pigment Violet 19; quinophthalone pigments: C.I. Pigment Yellow138; dioxazine pigments: C.I. Pigment Violet 23 and 37; flavanthronepigments: C.I. Pigment Yellow 24 (C.I. Vat Yellow 1); indanthronepigments: C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64 (C.I. Vat Blue6); isoindoline pigments: C.I. Pigment Orange 69; C.I. Pigment Red 260;C.I. Pigment Yellow 139 and 185; isoindolinone pigments: C.I. PigmentOrange 61; C.I. Pigment Red 257 and 260; C.I. Pigment Yellow 109, 110,173 and 185; isoviolanthrone pigments: C.I. Pigment Violet 31 (C.I. VatViolet 1); metal complex pigments: C.I. Pigment Yellow 117, 150 and 153;C.I. Pigment Green 8; perinone pigments: C.I. Pigment Orange 43 (C.I.Vat Orange 7); C.I. Pigment Red 194 (C.I. Vat Red 15); perylenepigments: C.I. Pigment Black 31 and 32; C.I. Pigment Red 123, 149, 178,179 (C.I. Vat Red 23), 190 (C.I. Vat Red 29) and 224; C.I. PigmentViolet 29; phthalocyanine pigments: C.I. Pigment Blue 15, 15:1, 15:2,15:3, 15:4, 15:6 and 16; C.I. Pigment Green 7 and 36; pyranthronepigments: C.I. Pigment Orange 51; C.I. Pigment Red 216 (C.I. Vat Orange4); thioindigo pigments: C.I. Pigment Red 88 and 181 (C.I. Vat Red 1);C.I. Pigment Violet 38 (C.I. Vat Violet 3); triarylcarbonium pigments:C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment Red81, 81:1 and 169; C.I. Pigment Violet 1, 2, 3 and 27; C.I. Pigment Black1 (aniline black); C.I. Pigment Yellow 101 (aldazine yellow); C.I.Pigment Brown 22;vat dyes (in addition to those already mentioned above):

C.I. Vat Yellow 2, 3, 4, 5, 9, 10, 12, 22, 26, 33, 37, 46, 48, 49 and50; C.I. Vat Orange 1, 2, 5, 9, 11, 13, 15, 19, 26, 29, 30 and 31; C.I.Vat Red 2, 10, 12, 13, 14, 16, 19, 21, 31, 32, 37, 41, 51, 52 and 61;C.I. Vat Violet 2, 9, 13, 14, 15, 17 and 21; C.I. Vat Blue 1 (C.I.Pigment Blue 66), 3, 5, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22, 25, 26,29, 30, 31, 35, 41, 42, 43, 64, 65, 66, 72 and 74; C.I. Vat Green 1, 2,3, 5, 7, 8, 9, 13, 14, 17, 26, 29, 30, 31, 32, 33, 40, 42, 43, 44 and49; C.I. Vat Brown 1, 3, 4, 5, 6, 9, 11, 17, 25, 32, 33, 35, 38, 39, 41,42, 44, 45, 49, 50, 55, 57, 68, 72, 73, 80, 81, 82, 83 and 84; C.I. VatBlack 1, 2, 7, 8, 9, 13, 14, 16, 19, 20, 22, 25, 27, 28, 29, 30, 31, 32,34, 36, 56, 57, 58, 63, 64 and 65;inorganic pigments:

white pigments: titanium dioxide (C.I. Pigment White 6), zinc white,pigment grade zinc oxide; zinc sulfide, lithopone; lead white; blackpigments: iron oxide black (C.I. Pigment Black 11), iron manganeseblack, spinel black (C.I. Pigment Black 27); carbon black (C.I. PigmentBlack 7); color pigments: chromium oxide, chromium oxide hydrate green;chrome green (C.I. Pigment Green 48); cobalt green (C.I. Pigment Green50); ultramarine green; cobalt blue (C.I. Pigment Blue 28 and 36);ultramarine blue; iron blue (C.I. Pigment Blue 27); manganese blue;ultramarine violet; cobalt violet and manganese violet; iron oxide red(C.I. Pigment Red 101); cadmium sulfoselenide (C.I. Pigment Red 108);molybdate red (C.I. Pigment Red 104); ultramarine red; iron oxide brown,mixed brown, spinal and corundum phases (C.I. Pigment Brown 24, 29 and31), chrome orange; iron oxide yellow (C.I. Pigment Yellow 42); nickeltitanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157 and164); chrome titanium yellow; cadmium sulfide and cadmium zinc sulfide(C.I. Pigment Yellow 37 and 35); chrome yellow (C.I. Pigment Yellow 34),zinc yellow, alkaline earth metal chromates; Naples yellow; bismuthvanadate (C.I. Pigment Yellow 184); interference pigments: metalliceffect pigments based on coated metal platelets; pearl luster pigmentsbased on mica platelets coated with metal oxide; liquid crystalpigments.

Preferred pigments in this context are monoazo pigments (especiallylaked BONS pigments, naphthol AS pigments), disazo pigments (especiallydiaryl yellow pigments, bisacetoacetanilide pigments, disazopyrazolonepigments), quinacridone pigments, quinophthalone pigments, perinonepigments, phthalocyanine pigments, triarylcarbonium pigments (alkaliblue pigments, laked rhodamines, dye salts with complex anions),isoindoline pigments and carbon blacks.

Examples of particularly preferred pigments are specifically: C.I.Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I.Pigment Blue 15:3 and 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 5,38 and 43 and C.I. Pigment Green 7.

These pigments are very useful for preparing ink-jet ink sets based oncolorant preparations according to the invention. The level of eachpigment in the individual inks shall be conformed to the respectiverequirements (e.g., trichromism).

The following pigment combinations are particularly recommended:

C.I. Pigment Yellow 138, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3and C.I. Pigment Black 7; C.I. Pigment Yellow 138, C.I. Pigment Red 122,C.I. Pigment Blue 15:3 or 15:4 and C.I. Pigment Black 7; C.I. PigmentYellow 138, C.I. Pigment Violet 19, C.I. Pigment Blue 15:3, C.I. PigmentBlack 7, C.I. Pigment Orange 43 and C.I. Pigment Green 7; C.I. PigmentYellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or 15:4, C.I.Pigment Black 7, C.I. Pigment Orange 5 and C.I. Pigment Green 7; C.I.Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Blue 15:3 or15:4, C.I. Pigment Black 7, C.I. Pigment Orange 38 and C.I. PigmentGreen 7; C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. PigmentBlue 15:3 or 15:4, C.I. Pigment Black 7, C.I. Pigment Orange 43 and C.I.Pigment Green 7.

The colorant preparations according to the invention generally includefrom 0.01 to 20% by weight, preferably from 0.2 to 10% by weight andmore preferably from 1 to 6% by weight of pigment, amounts in the rangefrom 1 to 6% by weight being particularly suitable.

The undissolved, dispersed pigments should be very finely divided.Preferably 95% and more preferably 99% of the colorant particles have anaverage particle diameter of 1 μm, preferably 0.5 μm and more preferablyup to 0.2 μm. The average particle diameter is preferably at least 0.05μm.

Water is the main constituent of the colorant preparations according tothe invention, preference being given to demineralized water asobtainable for example through the use of an ion exchanger. The watercontent is customarily in the range from 30 to 95% by weight. The watercontent of preparations according to the invention is preferably in therange from 40 to 60% by weight.

The colorant preparations according to the invention generally containfrom 0.1 to 40% by weight and preferably from 0.5 to 30% by weight ofpolyurethane block copolymers according to the invention.

The colorant preparations according to the invention may additionallyinclude one or more organic solvents. Low molecular weightpolytetrahydrofuran is a preferred additive, and it can be used alone orpreferably mixed with one or more high-boiling water-soluble or-miscible organic solvents.

The preferred polytetrahydrofuran customarily has an average molecularweight M_(w) of from 150 to 500 g/mol, preferably from 200 to 300 g/moland more preferably of about 250 g/mol. Polytetrahydrofuran ispreparable in known manner by cationic polymerization oftetrahydrofuran. The products are linear polytetramethylene glycols.

Other organic solvents used as an additive are generally high-boilingand hence water-retaining organic solvents that are soluble in ormiscible with water. High-boiling solvents have a boiling point>100° C.

Useful solvents include polyhydric alcohols, preferably branched andunbranched polyhydric alcohols containing from 2 to 8 and especiallyfrom 3 to 6 carbon atoms, such as ethylene glycol, 1,2-propylene glycol,1,3-propylene glycol or glycerol.

Useful solvents further include polyethylene glycols and polypropyleneglycols (which is also to be understood as meaning the lower polymers(di-, tri- and tetramers)) and their mono (especially C₁–C₆, inparticular C₁–C₄) alkyl ethers. Preference is given to polyethylene andpolypropylene glycols having average molecular weights of from 100 to1500 g/mol, in particular from 200 to 800 g/mol, mainly from 300 to 500g/mol. Examples are diethylene glycol, triethylene glycol, tetraethyleneglycol, diethylene glycol monomethyl ether, diethylene glycol monoethylether, diethylene glycol monopropyl ether, diethylene glycol monobutylether, triethylene glycol monomethyl ether, triethylene glycol monoethylether, triethylene glycol monopropyl ether, triethylene glycol monobutylether, di-, tri- and tetra-1,2- and -1,3-propylene glycol and di-, tri-and tetra-1,2- and -1,3-propylene glycol monomethyl, monoethyl,monopropyl and monobutyl ether.

Useful solvents further include pyrrolidone and N-alkyl-pyrrolidoneswhose alkyl chain preferably contains from 1 to 4, especially 1 or 2,carbon atoms. Examples of useful alkylpyrrolidones areN-methylpyrrolidone, N-ethylpyrrolidone andN-(2-hydroxyethyl)pyrrolidone.

Examples of particularly preferred solvents are 1,2-propylene glycol,1,3-propylene glycol, glycerol, sorbitol, diethylene glycol,polyethylene glycol (M_(w) from 300 to 500 g/mol), diethylene glycolmonobutyl ether, triethylene glycol monobutyl ether, pyrrolidone,N-methylpyrrolidone and N-(2-hydroxyethyl)-pyrrolidone.

The polytetrahydrofuran may also be mixed with one or more (e.g., two,three or four) of the abovementioned solvents.

The grinds according to the invention generally include from 0.1 to 40%by weight, preferably from 2.5 to 30% by weight, more preferably from 5to 25% by weight and most preferably from 10 to 20% by weight of solventcomponent.

The solvent component, including especially the particularly preferredsolvent combinations mentioned, may advantageously be augmented by urea(generally from 0.5 to 3% by weight, based on the weight of the colorantpreparation), which further enhances the water-retaining effect of thesolvent mixture.

The colorant preparations according to the invention may include furtherassistants of the type which are customary especially for aqueous inkjet inks and in the printing and coatings industry. Examples of suchassistants include preservatives such as for example1,2-benzisothiazolin-3-one (commercially available as Proxel brands fromAvecia Lim.) and its alkali metal salts, glutardialdehyde and/ortetramethylolacetylenediurea.

The present invention further provides for the use of the colorantpreparations according to the invention for producing aqueous inks forink jet printing, a process for producing inks for ink jet printingusing the colorant preparations according to the invention and the inksthus produced.

The inks according to the invention are produced by diluting thecolorant preparations according to the invention with water. As well aswater, further solvents and assistants can be added in the operation.

Water is the main constituent of the inks according to the invention,preference being given to demineralized water as obtainable for examplethrough the use of an ion exchanger. The water content is customarily inthe range from 50 to 95% by weight. The water content of inks accordingto the invention is preferably in the range from 60 to 80% by weight.

The inks according to the invention generally contain from 0.1 to 25% byweight and preferably from 0.5 to 10% by weight of polyurethane blockcopolymers according to the invention.

The inks according to the invention may include organic solvents as afurther component. Low molecular weight polytetrahydrofuran is apreferred additive, and it can be used alone or preferably mixed withone or more high-boiling water-soluble or water-miscible organicsolvents.

The preferred polytetrahydrofuran customarily has an average molecularweight M_(w) of from 150 to 500 g/mol, preferably from 200 to 300 g/moland more preferably of about 250 g/mol.

When polytetrahydrofuran is present in a mixture with further organicsolvents, the invention provides that the solvents used be high-boilingand hence water-retaining solvents that are soluble in or miscible withwater. High-boiling solvents have a boiling point>100° C.

Useful solvents include polyhydric alcohols, preferably branched andunbranched polyhydric alcohols containing from 2 to 8 and especiallyfrom 3 to 6 carbon atoms, such as ethylene glycol, 1,2-propylene glycol,1,3-propylene glycol or glyercol.

Useful solvents further include polyethylene glycols and polypropyleneglycols (which is also to be understood as meaning the lower polymers(di-, tri- and tetramers)) and their mono (especially C₁–C₆, inparticular C₁–C₄) alkyl ethers. Preference is given to polyethylene andpolypropylene glycols having average molecular weights of from 100 to1500 g/mol, in particular from 200 to 800 g/mol, mainly from 300 to 500g/mol. Examples are diethylene glycol, triethylene glycol, tetraethyleneglycol, diethylene glycol monomethyl ether, diethylene glycol monoethylether, diethylene glycol monopropyl ether, diethylene glycol monobutylether, triethylene glycol monomethyl ether, triethylene glycol monoethylether, triethylene glycol monopropyl ether, triethylene glycol monobutylether, di-, tri- and tetra-1,2- and -1,3-propylene glycol and di-, tri-and tetra-1,2- and -1,3-propylene glycol monomethyl, monoethyl,monopropyl and monobutyl ether.

Useful solvents further include pyrrolidone and N-alkyl-pyrrolidoneswhose alkyl chain preferably contains from 1 to 4, especially 1 or 2,carbon atoms. Examples of useful alkylpyrrolidones areN-methylpyrrolidone, N-ethylpyrrolidone andN-(2-hydroxyethyl)pyrrolidone.

Examples of particularly preferred solvents are 1,2-propylene glycol,1,3-propylene glycol, glycerol, sorbitol, diethylene glycol,polyethylene glycol (M_(w) from 300 to 500 g/mol), diethylene glycolmonobutyl ether, triethylene glycol monobutyl ether, pyrrolidone,N-methylpyrrolidone and N-(2-hydroxyethyl)-pyrrolidone.

The polytetrahydrofuran may also be mixed with one or more (e.g., two,three or four) of the abovementioned solvents.

The inks according to the invention generally contain from 0.1 to 40% byweight, preferably from 5 to 30% by weight, more preferably from 10 to25% by weight and most preferably from 10 to 20% by weight of solventcomponent.

The solvent components, including especially the aforementionedparticularly preferred solvent combinations, may advantageously besupplemented by urea (generally from 0.5 to 3% by weight, based on theweight of the colorant preparation), which further enhances thewater-retaining effect of the solvent mixture.

Useful additives further include erythritol, pentaerythritol, pentitolssuch as arabitol, adonitol and xylitol and hexitols such as sorbitol,mannitol and dulcitol.

The inks according to the invention may include further assistants ofthe type which are customary especially for aqueous ink jet inks and inthe printing and coatings industry. Examples of such assistants includepreservatives such as for example 1,2-benzisothiazolin-3-one(commercially available as Proxel brands from Avecia Lim.) and itsalkali metal salts, glutardialdehyde and/ortetramethylolacetylenediurea, Protectols®, antioxidants,degassers/defoamers (such as acetylenediols and ethoxylatedacetylenediols, which customarily contain from 20 to 40 mol of ethyleneoxide per mole of acetylenediol and also have a dispersing effect),viscosity regulators, flow agents, wetters (e.g., wetting surfactantsbased on ethoxylated or propoxylated fatty or oxo alcohols, propyleneoxide/ethylene oxide block copolymers, ethoxylates of oleic acid oralkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenyl phosphonates, alkyl phosphates, alkylphenylphosphates or preferably polyether siloxane copolymers, especiallyalkoxylated 2-(3-hydroxypropyl)heptamethyl trisiloxanes, which generallyhave a block of from 7 to 20 and preferably of from 7 to 12 ethyleneoxide units and a block of from 2 to 20 and preferably of from 2 to 10propylene oxide units and may be present in the colorant preparations inamounts of from 0.05 to 1% by weight), anti-settlers, luster improvers,lubricants, adhesion improvers, anti-skinning agents, delusterants,emulsifiers, stabilizers, water repellents, light control additives,hand improvers, antistats and bases such as triethanolamine or acids,especially carboxylic acids such as lactic acid or citric acid, forregulating the pH. If such assistants are part of the pigmentpreparations of the invention, their total amount is generally 2% byweight, especially 1% by weight, based on the weight of the colorantpreparation.

The inks according to the invention customarily have a dynamic viscosityof from 1 to 20 mPa·s and preferably from 2 to 15 mPa·s, as measuredusing a rotary viscometer from Haake in accordance with German standardspecification DIN 53019-1.

The surface tension of the inks according to the invention is generallyin the range from 24 to 70 mN/m and especially in the range from 30 to60 mN/m, as measured using a K 10 digital tensiometer from Krüss at roomtemperature. The pH of the colorant preparations according to theinvention is generally in the range from 5 to 10 and preferably in therange from 7 to 9, as measured using a 763 pH meter from Knick.

The inks according to the invention have a particularly low kinematicviscosity, especially when compared with inks containing a conventionalpolymeric binder.

The inks according to the invention may be formulated by mixing one ormore polyurethane block copolymers according to the invention withwater, with one or more pigments and with one or more melaminederivatives of the general formula V and also with or without additivesto form grinds as described above. However, it is possible for themelamine derivative or derivatives not to be added until the dilutionwith water and thus to the final formulation of the ink.

A further aspect of the present invention is a process for printingsheetlike or three-dimensional substrates by the ink jet process usingthe inks according to the invention. To this end, the colorantpreparations according to the invention are printed onto the substrate.

In the ink jet process, the typically aqueous inks are sprayed as smalldroplets directly onto the substrate. There is a continuous form of theprocess, in which the ink is pressed at a uniform rate through a nozzleand the jet is directed onto the substrate by an electric fielddepending on the pattern to be printed, and there is an interrupted ordrop-on-demand process, in which the ink is expelled only where acolored dot is to appear, the latter form of the process employingeither a piezoelectric crystal or a heated hollow needle (bubble jetprocess) to exert pressure on the ink system and so eject an inkdroplet. These techniques are described in Text. Chem. Color 19 (1987),No. 8, 23–29, and 21 (1989), No. 6, 27–32.

The inks of the invention are particularly useful as inks for thecontinuous jet process or the process employing a piezoelectric crystal.

The areas printed by the ink jet process are customarily treated withheat in order that the prints may be fixed and the dispersing bindersystem may be crosslinked. The heating may be effected using steam orhot air for example. A customary temperature range is from 150 to 180°C. for from 5 to 8 minutes. In the case of hot air, it is advisable totreat the printed textile at from 180 to 200° C. for about one minute.

A further embodiment of the present invention comprises a crosslinkingoperation initiated thermally or by actinic radiation, preferably in theUV region.

Useful substrate materials include:

coated or uncoated cellulosics such as paper, paperboard, cardboard,wood and woodbase, coated or uncoated metallic materials such as foils,sheets or workpieces composed of aluminum, iron, copper, silver, gold,zinc or alloys thereof, coated or uncoated silicatic materials such asglass, porcelain and ceramics, polymeric materials of any kind such aspolystyrene, polyamides, polyesters, polyethylene, polypropylene,melamine resins, polyacrylates, polyacrylonitrile, polyurethanes,polycarbonates, polyvinyl chloride, polyvinyl alcohols, polyvinylacetates, polyvinylpyrrolidones and corresponding copolymers and blockcopolymers, biodegradable polymers and natural polymers such as gelatin,textile materials such as fibers, yarns, threads, knits, wovens,nonwovens and garments composed of polyester, modified polyester,polyester blend fabrics, cellulosics such as cotton, cotton blendfabrics, jute, flax, hemp and ramie, viscose, wool, silk, polyamide,polyamide blend fabrics, polyacrylonitrile, triacetate, acetate,polycarbonate, polypropylene, polyvinyl chloride, polyester microfibersand glass fiber fabric, leather - both natural and artificial - in theform of smooth leather, nappa leather or suede leather, comestibles andcosmetics.

The inks according to the invention are notable for advantageousapplication properties, especially good start-of-print behavior and goodsustained use behavior (kogation) and also good drying characteristics.They produce printed images of high quality, i.e., high brilliance anddepth of shade and also high rubfastness, lightfastness, waterfastnessand wetrubfastness. They are particularly useful for printing coated anduncoated paper and also textile. It is particularly advantageous thatthe subject process for printing textiles can be performed particularlyrapidly and at high throughput per unit time. It was also found thatfixation of the print is excellent even after several washes. Similarly,fixation is excellent even in the case of substrates which are singly orrepeatedly bent, folded or creased.

The present invention further provides substrates, especially textilesubstrates, which have been printed by one of the abovementionedprocesses according to the invention and are notable for particularlycrisply printed images or drawings possessing excellent fixation.

The dispersing binder systems according to the invention are also usefulin high solids coating systems. The dispersing binder systems accordingto the invention are further useful in no solvent or low solventcoatings, i.e., coatings containing less than 5% by weight of solvent,and in nonaqueous inks. A further aspect of the present invention istherefore the use of the dispersing binder systems according to theinvention in high solids coating systems, in no solvent or low solventcoatings and also in nonaqueous inks. A further aspect of the presentinvention is high solids coating systems, no solvent or low solventcoatings and nonaqueous inks that contain the dispersing binder systemsaccording to the invention.

The colorant preparations of the invention are very useful insolvent-containing coatings, solvents in this context being nonaqueoussolvents, and in waterborne coatings.

A further, very particularly preferred subject matter of the presentinvention is the use of the dispersing binder systems of the inventionas a dispersing binder additive for pigment dyeing and pigment printing.

According to the invention, the above-described grinds are used toprepare a dyeing liquor for pigment dyeing or a print paste for pigmentprinting, specifically textile pigment printing. The present inventionaccordingly further provides a process for preparing dyeing liquors forpigment dyeing and for preparing print pastes for pigment printing andalso the dyeing liquors and print pastes according to this invention.

The process of this invention comprises mixing the grinds of thisinvention with the assistants required for the dyeing or printingoperation and adjusting the colorant content by diluting with water.

The water used for this purpose need not be completely ion-free. It iscustomary to use incompletely deionized water or very soft water. Ifinsufficiently soft water is available, it is customary to usecomplexing agents (water softeners) to control the hardness in thewater. Useful water softeners for the pigment dyeing operation generallysequester Ca²⁺ and Mg²⁺ ions. Examples of particularly useful watersofteners are nitrilotriacetic acid, ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriaceticacid or methylglycinediacetic acid. The amount of water added to preparethe dyeing liquor depends on the depth of shade to be produced on thetextile on the one hand and the amount of dyeing liquor padded onto thetextile on the other.

Dyeing liquors according to this invention may further includeadditives, for example solvents. Useful solvents include the samesolvents as are useful for preparing the grinds. Preference is given toconcentrations from 0 to 10% by weight, particularly preferably up to 5%by weight.

The dyeing liquors of this invention may further include a wetting agentadditive, preferably a wetting agent of the low-foam type, since foamingdue to the high turbulence of the dyeing operation impairs the qualityof the dyeing by producing unlevelness. Wetting agents used include forexample ethoxylated and/or propoxylated products of fatty alcohols orpropylene oxide-ethylene oxide block copolymers, ethoxylated orpropoxylated fatty or oxo alcohols, also ethoxylates of oleic acid oralkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenyl phosphonates, alkyl phosphates and alkylphenylphosphates.

Dry woven or loop-formingly knitted textiles as used in continuouspigment dyeing contain a large amount of air. Dyeing here requires theuse of deaerators. These are based for example on polyether siloxanecopolymers. They can be included in the dyeing liquors of this inventionin amounts from 0.01 to 2 g/l.

The dyeing liquors according to this invention may further include oneor more hand improvers. These are generally polysiloxanes or waxes(based on polyethylene or polyethylene glycols). Polysiloxanes have theadvantage of permanence, whereas waxes are gradually washed off duringuse.

The dyeing liquors according to this invention customarily have a weaklyacidic pH, preferably in the range from 4 to 6.5. The viscosities of thedyeing liquors according to this invention are preferably in the rangebelow 100 mPa·s. The surface tensions of the dyeing liquors according tothis invention are to be adjusted so as to enable fabric to be wet.Surface tensions of less than 50 mN/m are widely used.

A further aspect of the present invention is a process for preparing thedyeing liquors according to this invention. The process according tothis invention comprises mixing the above-described grinds with theabove-recited additives such as further solvents, defoamers, handimprovers, emulsifiers and/or biocides and making up with water at from0 to 100° C. and customarily at atmospheric pressure. The processcustomarily comprises the components being stirred in a mixing vessel,the size and shape of which are not critical. The stirring is preferablyfollowed by a clarifying filtration.

A further aspect of the present invention is a process for dyeingtextile substrates using the above-described dyeing liquors according tothis invention. The process can be carried out in the usual machines.Preference is given to pad-mangles consisting essentially of two niprolls through which the textile is passed. The liquor sits above therolls and wets the textile. The nip pressure causes the textile to besqueezed off and ensures a constant add-on.

The actual dyeing step is customarily followed by thermal drying andfixing steps. Preferably, the fabric is dried at from 100 to 110° C. forfrom 30 seconds to 3 minutes and fixed at from 150° C. to 190° C. forfrom 30 seconds to 5 minutes. The drying and fixing causes thedispersing binder additives used according to this invention to becrosslinked. Preference is given to a process for pigment dyeing bypadding. The printed and dyed substrates are notable for particularbrilliance of color coupled with outstanding hand. A further aspect ofthe present invention accordingly relates to substrates dyed by theabove-described process using the dyeing liquors according to thisinvention.

A further aspect of the present invention is the use of theabove-described dispersing binder additives for textile printing.According to this invention, the above-described dispersing binderadditives are incorporated into a print paste for this purpose.Advantageously, the textile printing paste according to this inventionis prepared from the grinds according to this invention by mixing withcustomary printing assistants and subsequent adjustment of the colorantcontent by dilution with water. The print paste is customarily preparedat from 0 to 200° C. and at from 1 to 10 bar.

Useful printing assistants are known, cf. for example Ullmann'sEnyclopädie der technischen Chemie, 4th Edition, Textildruck, Volume 22,pages 565 ff., Verlag Chemie, Weinheim, Deerfield/Florida, Basle; 1982.Examples of useful printing assistants are thickeners, fixers, handimprovers and emulsifiers.

Natural and synthetic thickeners can be used. Preference is given to theuse of synthetic thickeners, for example generally liquid solutions ofsynthetic polymers in for example white oil or as aqueous solutions. Thepolymers contain acid groups which are neutralized with ammoniacompletely or to a certain percentage. The fixing operation releasesammonia, whereby the pH is lowered and the actual fixing starts.

The ready-prepared paste according to this invention may contain from 30to 70% by weight of white oil. Aqueous thickeners customarily contain upto 25% by weight of polymer. When aqueous formulations of the thickenerare to be used, it is customary to add aqueous ammonia. Similarly, theuse of granular, solid formulations of the thickener is conceivable inorder that pigment prints may be produced with zero emissions.

The pastes according to the invention may include a further fixingagent. The inclusion of fixing agents in print pastes is known per se.Known and highly suitable fixing agents are commercially available underthe names Acrafix RF® (from Bayer AG), Helizarin Fixierer S® andHelizarin Fixierer LF® (BASF Aktiengesellschaft) and Tabriprint FixiererR® (from CHT).

The print pastes according to this invention may further include handimprovers, which are customarily selected from silicones, especiallypolydimethylsiloxanes, and fatty acid esters. Examples of commerciallyavailable hand improvers useful for inclusion in the print pastesaccording to this invention are Acramin® Weichmacher SI (Bayer AG),Luprimol SIG® and Luprimol CW® (BASF Aktiengesellschaft).

The print pastes according to this invention may further include one ormore emulsifiers, especially when the pastes contain thickenerscontaining white oil and are obtained as an oil-in-water emulsion.Examples of suitable emulsifiers include aryl- or alkyl-substitutedpolyglycol ethers. Commercially available examples of suitableemulsifiers are Emulgator W® (Bayer), Luprintol PE New® and LuprintolMP® (BASF Aktiengesellschaft) and Solegal W® (Hoechst AG).

Further possible ingredients include Brønsted acids, which are neededparticularly in the case of nonaqueous-based pastes. Preference is givento ammonium salts of inorganic acids, for example diammoniumhydrogenphosphate.

Pigment printing can be carried out by various processes known per se.It is customary to use a screen through which the print paste is forcedwith a squeegee. This process belongs to the screen printing processes.The subject pigment printing process utilizing the print pastesaccording to this invention provides printed substrates combiningparticularly high brilliance and depth of shade for the prints withexcellent hand for the printed substrates. The present inventionaccordingly also provides substrates printed by the subject processutilizing the subject print pastes. The actual printing step iscustomarily followed by thermal drying and fixing steps. Preferably, thefabric is dried at from 80 to 110° C. for from 30 seconds to 3 minutesand fixed at from 150° C. to 190° C. for from 30 seconds to 5 minutes.The drying and fixing causes the dispersing binder additive usedaccording to this invention to be crosslinked.

Useful substrate materials include textile materials such as fibers,yarns, threads, knits, wovens, nonwovens and garments composed ofpolyester, modified polyester, polyester blend fabric, cellulosicmaterials such as cotton, cotton blend fabric, jute, flax, hemp andramie, viscose, wool, silk, polyamide, polyamide blend fabric,polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene,polyvinyl chloride, polyester microfibers and glass fiber fabric.

The examples which follow illustrate the invention.

1. SYNTHESIS EXAMPLES 1.1. SYNTHESIS OF THE A BLOCK

142.86 g of the Lupraphen® VP9327 polyesterdiol from BASF Schwarzheidewere dissolved with 18.52 g (0.178 mol) of neopentylglycol, commerciallyavailable from Acros Chemicals, 19.26 g of dimethylolpropionic acid(0.144 mol), commercially available from Acros Chemicals, and 107.02 g(0.423 mol) of 4,4′-diphenylmethane diisocyanate (Lupranat® MES fromBASF Aktiengesellschaft) in 287.7 g (324 ml) of tetrahydrofuran whichhas been distilled over sodium and, after addition of 0.05 g ofdi-n-butyltin dilaurate (Bärostab® DBTL/C from Bärlocher GmbH), heatedto 60° C. After isocyanate was no longer detectable by IR spectroscopy,the reaction was ended by cooling.

1.2. SYNTHESIS OF THE B BLOCK

52.0 g (0.483 mol) of neopentylglycol and 178.45 g (0.665 mol) ofm-tetramethylxylene diisocyanate (commercially available from CytecGmbH) were dissolved in 230.45 g (260 ml) of tetrahydrofuran and, afteraddition of 0.13 g of di-n-butyltin dilaurate, heated to 60° C. untilthe titrimetrically determined isocyanate content was 4.2% by weight.

The isocyanate was titrimetrically determined by admixing an aliquot ofthe reaction solution with an excess of di-n-butylamine, so that theunconsumed isocyanate groups fully reacted, and backtitrating theunconverted amine. The method is known to those skilled in the art ofpolyurethane chemistry.

1.3. CONVERSION TO THE ABA BLOCK COPOLYMER OF THE GENERAL FORMULA I

100 g of the B block solution described under 1.2. were mixed with 800 gof the A block solution described under 1.1. and, after addition of 0.2g of di-n-butyltin dilaurate, heated to 60° C. When isocyanate was nolonger titrimetrically detectable, the dimethylolpropionic acidincorporated in the A block was neutralized by addition of 20.2 g oftriethylamine and then 835 ml of water were added. The dispersion thusformed was distilled to remove the tetrahydrofuran.

2. PRODUCTION OF A COLORANT PREPARATION

6.0 g of Pigment Blue 15:4 were ball milled (Dispermat AE 3-C from VAMGetzmann) with 43.27 g of a 41.6% by weight solution of the blockcopolymer prepared under 1.3. and 4.07 g of the Cymel® 327 melaminederivative from Cytec GmbH and also 3.0 g of 1,2-propylene glycol and0.03 g of 1,2-benzisothiazolin-3-one (10% by weight in 1,2-propyleneglycol) to an average particle size of 189 nm for the pigment(determined by laser diffraction using a Coulter LS 230 from Coulter).The grinding media were then separated off.

3. PRODUCTION OF AN INK FOR THE INK JET PROCESS AND PRINTING OFSUBSTRATES

20 g of the colorant preparation described under 2. were stirred with

6.0 g of polytetrahydrofuran of molar mass 250, commercially availablefrom BASF Aktiengesellschaft;

3.0 g of triethylene glycol n-butyl ether

5.0 g of polyethylene glycol of molar mass 400

6.0 g of glycerol

1.0 g of urea

0.5 g of TegoWet260® surfactant and

0.5 g of 1,2-benzisothiazolin-3-one (10% by weight in 1,2-propyleneglycol)

and also 58 ml of water in a glass beaker. This afforded 100 g of anink. The viscosity was 3.92 mPa·s and the pH was 8.14.

The ink described above was used on a commercially available printerfrom Epson (Stylus Color 3000) to uniformly print an area 25.5 cm×18 cmin size at a resolution of 720 dpi. The substrates used were paper andpaper-laminated cotton. There was no nozzle failure by the time 15 pageshad been printed. The printed textile was fixed by storage in a dryingcabinet at 150° C. for 5 minutes and was then tested for its performancecharacteristics:

The use of the gray scale to determine the fastnesses is described inISO 105 A03 (DIN 54002, rubfastness) and IS0105-A02 (DIN 54001,washfastness).

Rubfastness dry: 3–4

Rubfastness wet: 3

Washfastness: 4

4. PRODUCTION OF A COLORANT PREPARATION

-   -   6.0 g of Pigment Yellow 138 were ball milled in a Scandex shaker        from Lau with 43.27 g of the aqueous solution of block copolymer        prepared under 1.3 and 4.07 g of Cymel® 327 from Cytec GmbH and        also 3.0 g of propylene glycol as an organic solvent and 0.03 g        of 1,2-benzisothiazolone as a 10% by weight solution in        propylene glycol and also 4.68 ml of water to an average        particle size of 200 nm for the pigment (determined by laser        diffraction using a Coulter LS 230 from Coulter). The grinding        media were then separated off. This provided a unitary grind.

5. PRODUCTION OF A DYEING LIQUOR

-   -   33 g of the grind described in Example 4 were mixed in a beaker        with 3 g of poly-THF 250 (commercially available from BASF        Aktiengesellschaft), 1.5 g of triethylene glycol mono-n-butyl        ether, 2.5 g of polyethylene glycol having an average molar mass        M_(w) of 400 g, 3 g of glycerol, 0.5 g of urea, 0.5 g of Cymel®        327 melamine resin from Cytec GmbH and also 0.25 g of Tego Wet        260 surfactant and 0.25 g of 1,2-benzisothiazolone as a 10% by        weight solution in propylene glycol and made up with water to        100 g. The dyeing liquor thus obtained was clarified by passing        it through a filter (having a pore diameter of 1 μm).

6. PIGMENT DYEING WITH DYEING LIQUOR OF INVENTION

-   -   The dye liquor obtained in Example 5 was applied to a 67:33        polyester-cotton fabric on an HVF12085 pad-mangle from Mathis.        The nip pressure of the rolls was 2.6 bar. The result was a wet        pickup of 55%. The application rate was 2 m/min. The textile was        then dried at 110° C. in an LTF89534 Mathis circulating air        cabinet at 50% recirculation for 60 s. The final fixing took        place at 190° C. and 100% recirculation in the course of 30 s.

The following fastnesses were determined:

Brush wash 4–5 Rubfastness dry 4–5 Rubfastness wet 4 Wash fastness 4

7. PRODUCTION OF A PRINT PASTE

-   -   33 g of the grind described in Example 4 were stirred in a        beaker with 3 g of poly-THF 250 (commercially available from        BASF Aktiengesellschaft), 1.5 g of triethylene glycol        mono-n-butyl ether, 2.5 g of polyethylene glycol having an        average molar mass M_(w) of 400 g, 3 g of glycerol, 0.5 g of        urea, 0.5 g of Cymel® melamine resin from Cytec GmbH and also        0.25 g of Tego Wet 260 surfactant and 0.25 g of        1,2-benzisothiazolone as a 10% by weight solution in propylene        glycol and made up with water to 100 g. This thus obtained        pigment paste was admixed with 2.8 g of Lutexal HIT thickener        from BASF Aktiengesellschaft by rapid stirring with a high speed        stirrer. The print paste thus obtained had a viscosity of 6.5        Pas.

8. PIGMENT PRINTING WITH PRINT PASTE OF INVENTION

-   -   The print paste obtained in Example 7 was printed through a 120        mesh screen printing stencil onto a cotton fabric using a roller        squeegee 8 mm in diameter and a tension setting of 6. The        textile was then dried at 80° C. in an LTF89534 Mathis        circulating air cabinet at 50% recirculation for 5 min. The        final fixing took place at 150° C. and 100% recirculation in the        course of 5 min.

The following fastnesses were determined:

Rubfastness dry 4 Rubfastness wet 3–4 Wash fastness 4–5

-   -   Rubfastnesses were determined in accordance with ISO 105 X12 and        the wash fastness was determined in accordance with ISO 105 C2.

1. A polyurethane block copolymer of the general formulae I to IV

where: A is a polyurethane block containing at least one hydrophilic endgroup X¹ which is terminated by OH, SH, NH2 or NHR, where R is selectedfrom C₁–C₁₂-alkyl or C₆–C₁₄-aryl, B is a hydrophobic polyurethane blockfrom which hydrophilic end groups X¹ are absent, X¹ and X² are each ahydrophilic end group, X¹ being a carboxyl group or being an SO3 groupintroduced by incorporation of a sulfo-containing diol, each X² beingthe same or different and being selected from the group consisting of—OH, O(CH₂—CH₂—O)_(x)—H, —O(—CHCH₃—CH₂—O)_(x)—H, —O(—CH₂—CHCH₃—O)_(x)—H,and —O(—CH₂—CH₂—CH₂—CH₂—O)_(x)—H, where x is an integer from 1 to 20,and n is an integer from 1 to
 20. 2. A polyurethane block copolymer asclaimed in claim 1, wherein said blocks A and B each have a formulaweight M_(n) in the range from 600 to 30,000 g.
 3. A crosslinkabledispersing binder system, comprising at least one polyurethane blockcopolymer, as claimed in claim
 2. 4. A process for producing acrosslinkable dispersing binder system, which comprises mixing one ormore polyurethane block copolymers as claimed in claim 2 with one ormore melamine derivatives of the general formula V

where: R¹ to R⁶ are the same or different and are each selected from thegroup consisting of hydrogen, CH₂—OR⁷, CH(OR⁷)₂ and CH₂—N(R⁷)₂, whereeach R⁷ may be the same or different and is selected from the groupconsisting of hydrogen, branched C₁–C₁₂-alkyl, unbranched C₁–C₁₂-alkyl,and alkoxyalkylene selected from the group consisting of(—CH₂—CH₂—O)_(m)—H, (—CHCH₃—CH₂—O)_(m)—H, (—CH₂—CHCH₃—O)_(m)—H, and(—CH₂—CH₂—CH₂—CH₂—O)_(m)—H, where m is an integer from 1 to
 20. 5. Adispersing binder system obtained by the process of claim
 4. 6. Adispersing binder system as claimed in claim 5, wherein R¹ and R² areboth hydrogen.
 7. A dispersing binder system as claimed in claim 5,wherein R³ is CH₂OH.
 8. A colorant preparation comprising a dispersingbinder system as claimed in claim 3, water and a finely dividedinorganic or organic pigment.
 9. An ink for the ink jet process,comprising a colorant preparation as claimed in claim
 8. 10. The processfor printing a sheetlike or three-dimensional substrate by the ink jetprocess comprising printing with an ink as claimed in claim
 9. 11. Asheetlike or and three-dimensional substrate obtained by the process ofclaim
 10. 12. A high solids coating, which comprises: the dispersingbinder system as claimed in claim
 5. 13. A high solids coating systemcomprising the dispersing binder system as claimed in claim
 5. 14. Themethod of preparing a coating, which comprises adding a solvent to thecolorant preparation of claim
 8. 15. A solvent containing coatingcomprising a colorant preparation as claimed in claim 8 admixed with asolvent.
 16. A composition selected from the group consisting of asolvent or low solvent coating composition or no solvent or low solventpaint comprising the dispersing binder system of claim
 5. 17. Thepreparation of a waterborne coating comprising admixing the colorantpreparation of claim 8 with water.
 18. A waterborn coating comprising acolorant preparation as claimed in claim
 8. 19. The method whichcomprises preparing a non-aqueous ink by admixing the dispersing bindersystem of claim 5 with a nonaqueous solvent.
 20. A nonaqueous inkcomprising the dispersing binder system as claimed in claim
 5. 21. Thepreparation of a pigment dyeing or printing composition comprisingadmixing the crosslinkable dispersing binder system as claimed in claim5 with a pigment as a dispersing binder for said pigment dyeing andpigment printing.
 22. The process of claim 21, wherein said blocks A andB in said polyurethane block copolymers each have a formula weight M_(n)in the range from 600 to 10,000 g.
 23. Pigment dyeing liquors containinga pigment and a dispersing binder additive prepared as set forth inclaim
 21. 24. A process for preparing a pigment dyeing liquor as claimedin claim 23, which comprises stirring up with each other followed byclarification of grinds comprising a finely divided pigment and adispersing binder additive, and water and optionally also one or moreingredients selected from the group consisting of solvents, defoamers,hand improvers and biocides.
 25. The process for dyeing a substratecomprising dyeing with a pigment dyeing composition containing adispersing binder additive prepared as set forth in claim
 21. 26. Asubstrate dyed by a process as claimed in claim
 25. 27. A pigmentprinting paste containing a dispersing binder additive prepared as setforth in claim
 21. 28. A process for preparing a pigment printing pasteas claimed in claim 27, which comprises stirring up with each othergrinds comprising a finely divided pigment and a dispersing binderadditive, and water and optionally also one or more ingredients selectedfrom thickeners, fixatives, hand improvers, emulsifiers and Brønstedacids.
 29. The process for printing a substrate comprising printing witha pigment printing composition containing a dispersing binder additiveprepared as set forth in claim
 21. 30. A substrate printed by a processas claimed in claim
 29. 31. The process for dyeing a substratecomprising dyeing with pigment dyeing liquor containing a dispersingbinder additive as set forth in claim
 23. 32. The polyurethane blockcopolymer of claim 2, wherein block A is a polyester diol, neopentylglycol, dimethylolpropionic acid, diphenylmethane diisocyanate reactionproduct polyurethane and block B is a neopentyl glycol-tetramethylxylenediisocyanate reaction product polyurethane.